Self-Assembly of Synthetic and Biological Polymeric Systems of ...

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therefore, characteristic of solid crystalline polymers. Hence, when the concept of macromolecular conformation is limited to a single macromolecule, it defines the polymer`s secondary structure. Figure 1.5. Secondary structure of polymers. 1.3.3.- Tertiary Structure. Macromolecular conformation related to several macromolecules arranged together in any liquid or solid phase defines the polymer´s tertiary structure. Usual tertiary structures are depicted in Figure 1.6. These can be represented either by a tight arrangement of random coil chains (spaghetti-like structure) as in molten or amorphous solid polymer; by a fringed-micelle structure as observed in semi-crystalline solid polymers; or in regularly folded chains or super- helix tertiary structures as in the case of highly crystalline solid polymers. Figure 1.6. Tertiary structure of polymer. Any polymeric material in the solid state posses great amounts of polymeric molecules in the form of aggregates. The process of molecular aggregation can lead to the formation of either crystalline or amorphous materials, which depend on both the polymer molecular structure 22
and the available configurations of the polymeric backbone´s building blocks. The ability of polymer chains to establish a sufficient high number of dipole-dipole interactions, hydrogen bonding, or van der Waals interactions, amongst others, is also a key factor in promoting and controlling the molecular aggregation process in spite of the energy involved in this kind of intermolecular forces is very weak (0.5-10 kcal/mol) if compared with covalent bonds (50-100 kcal/mol) 1.4.- Molecular self-assembly. Molecular self-assembly is a spontaneous process by which molecules interact with each other to form well-ordered supramolecular structures. The self-association between molecular building blocks is mediated through non-covalent association of molecules (molecular recognition processes). In this way, extraordinarily complex assemblies are formed in various natural systems, and synthetic preformed molecular building blocks are assembled together by keeping a delicate balance between non-covalent repulsive and attractive interaction by using forces such as van der Waals and ionic interactions, metal coordination, H-bonding, π-π interactions or hydrophobic forces. This process has motivated many different studies in the fields of nanotechnology and materials science based on the design of new functional nanostructures (6)(7). The only requirement for self-assembly is that the building block should contain moieties able to establish non-covalent interactions in specific environments (6)(7). Thus, advanced self-assembled nanomaterials have already been prepared from many different types of molecules such as lipids, synthetic peptides, nucleic acids, low molecular weight surfactants, dendrons, transition metals, inorganic nanoparticles or polymers (8)(9). The latter have recently received great attention due to their increasingly scientific importance and vast utility in a wide range of technological applications by their ability to spontaneously self-organize into well-ordered aggregates, either in the solid state or in semidilute and dilute solutions (9)(10). Nowadays, the self-organization of molecular building blocks is probably one of the most prominent topics of modern sciences. Indeed, supramolecular self-assembly is the key strategy of Nature for fabricating multifunctional structures such as enzymes, ribosomes, membranes channel or transport proteins from rather simple molecules such peptides, sugars and lipids. For instance, Nature produces complex intermolecular structures with biomolecules, through the control of biomolecular primary, secondary, tertiary and quaternary structure. The 23
Page 1: Grupo de Física de Coloides y Pol
Page 5: Agradecimientos A mi Familia A mi P
Page 9: v List of papers I. Self-assembly p
Page 12 and 13: 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.
Page 14 and 15: 5.4 5.5 5.3.2 5.5.1 Chapter 6 Kinet
Page 16 and 17: amiloides de la proteína albúmina
Page 18 and 19: vesiculares son el resultado de la
Page 20 and 21: origina debido a condiciones ambien
Page 22 and 23: con las fibras vecinas más cercana
Page 25 and 26: Abstract In the present work, we in
Page 27: [Au]/[protein] molar ratio and numb
Page 30 and 31: synthetic polymers are obtained fro
Page 32 and 33: On the other hand, in terms of chem
Page 34 and 35: Additionally, to obtain a better kn
Page 38 and 39: presence of electrostatic charge in
Page 41 and 42: Contents 2.1 2.2 2.3 2.4 2.5 2.6 2.
Page 43 and 44: where w is the meniscus’ weight d
Page 45 and 46: that they exert little force one on
Page 47 and 48: This oscillating dipole acts as an
Page 49 and 50: (APD) and its associated optics (pi
Page 51 and 52: where r is the distance of the dipo
Page 53 and 54: When , the former equation can be s
Page 55 and 56: autocorrelation function (ACF). In
Page 57 and 58: and, therefore, . The autocorrelati
Page 59 and 60: A transmission electron microscope
Page 61 and 62: 2.5.- Atomic force microscopy (AFM)
Page 63 and 64: ecause of the energy loss in the ex
Page 65 and 66: Figure 2.15. Schematic representati
Page 67 and 68: ackbone of proteins. Since proteins
Page 69 and 70: According to classical mechanics, t
Page 71 and 72: chemical composition, configuration
Page 73 and 74: 2.9.1.- Viscoelasticity Many materi
Page 75 and 76: where is the total strain rate, whi
Page 77 and 78: Using equations 2.40 and 2.41 in eq
Page 79 and 80: scattering process that incoming X-
Page 81 and 82: maximum intensity of the peak, Imax
Page 83 and 84: translation of the reciprocal latti
Page 85 and 86: For a single crystal, the chance to
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excitation; namely, a valance elect
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Figure 2.27. Distinction between si
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microscope, there are two polarized
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In particular, we use SQUID to meas
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are aligned by means of an external
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on the digital profile of a drop im
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Laser confocal microscopy. Confocal
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Fluorescence spectroscopy. Fluoresc
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Superconducting quantum interferenc
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temperatures, the chains are mixed
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e detected by a given method. Therm
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subsequently, of their thermodynami
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a) O b) H 2C CH 2 O H 2C CH Figure
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Contents 4.1 4.2 4.3 4.3.1 CHAPTER
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7108 Langmuir, Vol. 24, No. 14, 200
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7110 Langmuir, Vol. 24, No. 14, 200
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7112 Langmuir, Vol. 24, No. 14, 200
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7114 Langmuir, Vol. 24, No. 14, 200
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7116 Langmuir, Vol. 24, No. 14, 200
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15704 J. Phys. Chem. C, Vol. 114, N
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4.3.1.- Relevant aspects I. For E12
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Contents 5.1 5.2 5.3 5.4 5.5 5.1.1
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acids whose lateral side chains cha
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adjacent segments of an antiparalle
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5.2.1.- Unfolded state Over the las
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5.2.4.- Energy landscape: protein a
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molecular medicine viewpoint, prote
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shows the typical nucleation-depend
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the energy landscape of the aggrega
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exposed loop region. The secondary
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Biophysical Journal Volume 96 March
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Fibrillation Pathway of HSA 2355 q
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Fibrillation Pathway of HSA 2357 mo
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Fibrillation Pathway of HSA 2359 in
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Fibrillation Pathway of HSA 2361 Fu
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Fibrillation Pathway of HSA 2363 FI
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Fibrillation Pathway of HSA 2365 Wh
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Fibrillation Pathway of HSA 2367 of
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Fibrillation Pathway of HSA 2369 17
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Influence of Electrostatic Interact
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Fibrillation Process of Human Serum
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12392 J. Phys. Chem. B, Vol. 113, N
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5 10 15 20 25 30 35 40 45 Soft Matt
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5 10 15 20 25 r h,app = kT/(6πηD
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5 10 15 20 25 30 35 40 45 50 below,
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5 10 15 20 25 30 55 Figure 3: Selec
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10 15 Soft Matter Cite this: DOI: 1
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5 10 15 Soft Matter Cite this: DOI:
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5 65. L. A. Sikkink, M. Ramirez-Alv
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ions would interact electrostatical
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pubs.acs.org/JPCL Figure 3. (a) Tim
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(54) Almeida, N. L.; Oliveira, C. L
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netospirillum magneticum strain AMB
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One-Dimensional Magnetic Nanowires
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temperatures, and solvent polarity.
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Conclusions The work has two parts:
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equire a highly organized and unsta
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References 1. Hiemenz, Paul C. Poly
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33. Wang, Z. L. HANDBOOK OF MICROSC
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67. Polymers Get Organized. Bucknal
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94. Are there Pathways for Protein
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123. Designing conditions for in vi
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151. SERS-based diagnosis and biode
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